US8048511B2 - Titanium oxide coating agent and titanium oxide film forming method - Google Patents

Titanium oxide coating agent and titanium oxide film forming method Download PDF

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US8048511B2
US8048511B2 US11/885,918 US88591805A US8048511B2 US 8048511 B2 US8048511 B2 US 8048511B2 US 88591805 A US88591805 A US 88591805A US 8048511 B2 US8048511 B2 US 8048511B2
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titanium oxide
coating agent
film
microparticles
thin sheet
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US20080280103A1 (en
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Hiroshi UETSUKA
Tetsuya Shichi
Koji Oshika
Akira Fujishima
Katsuhiko Takagi
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Central Japan Railway Co
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Central Japan Railway Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/054—Forming anti-misting or drip-proofing coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0018—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings uncoated and unlayered plate-like particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic compounds
    • C09C1/3661—Coating
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24413—Metal or metal compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

  • This invention relates to coating agents and coating methods capable of forming photocatalytic titanium oxide film with strong adhesion, a high degree of smoothness and a high degree of hardness, on a substrate made of materials such as glass, plastics, metals, and ceramic.
  • the present invention also relates to such coatings.
  • Photocatalytically active titanium oxide is applied in a broad range of areas because titanium oxide is a material with anti-staining/fouling, anti-bacterial and odor eliminating properties, upon radiation by sun light or ultra-violet light.
  • Photocatlytic titanium oxide is usually made of spherical microparticles in the range of a few nm to several tens of nm.
  • a suitable fixing agent P 3 which is called a binder.
  • photocatlytic titanium is used as a coating agent. material.
  • the binder is selected depending on a type of the base material to be coated.
  • Inorganic binder such as silica or silicate, or organic binder, such as silicone resin or fluorine resin, which are resistant to the photocatalytic reaction, are used.
  • organic binder such as silicone resin or fluorine resin, which are resistant to the photocatalytic reaction.
  • titanium oxide sol obtained from hydrolyzing titanium tetra alkoxide, such as Ti(OC 3 H 7 ) 4 is used as a coating agent.
  • Titanium oxide is also used in the form of sol solution wherein sheet-like microparticles of titanium oxide (titanium oxide nanosheets) are dispersed.
  • This sol solution can be obtained by acidifying titanate compound having a layer structure and subsequently treating the titanate compound in aqueous solution of ammonium compound or amine compound (Patent Document 1 to 5).
  • Patent Document 6 For a coating method with the titanium oxide nanosheets, super-thin film methods wherein the super-thin film is layered by alternately immersing a base material into the solution of cationic polymer and solution of nanosheets (Patent Document 6 to 9), anatase type or rutile type titanium oxide methods wherein these types of titanium oxide is heated so as to obtain an anatase type or rutile type titanium oxide film (Patent Document 6 and 10), or a film forming method wherein layers are formed according to Langmuir-Blodgett method (BL method) (Patent Document 11) are known.
  • BL method Langmuir-Blodgett method
  • the binder had a low chemical stability and low resistance against physical impact (a low hardness) applied by dust and the like, and that forming a thin film was difficult without losing the color, texture or transparency of the base material.
  • the present invention is made so as to attain the above-described objects.
  • the purpose of the invention is to provide the coating agent, which can simply form a film over a large area, is chemically and physically stable, can form a smooth film, expresses the advantageous hydrophilic property and ability to decompose fouling, and can form an ultrathin film, to provide such film, and to provide a method of forming such film. It is also the purpose of the present invention to provide glass products, metal products, ceramic products, and heat-resistant polymer products produced with such coating agent with the film and the film forming method.
  • the invention in claim 1 is related to a coating agent containing thin sheet microparticles of titanium oxide.
  • thin sheet microparticles of titanium oxide are sheet-like particles formed from layered titanate that is exfoliated into single layers.
  • the particles have thickness of less than 1 nm with a high aspect ratio.
  • the coating agent of the present invention can be manufactured by mixing this kind of sheet-like titanium oxide with, for example, silica sol prepared by hydrolyzing tetra alkoxysilane, with titania sol obtained from hydrolyzing titanium tetra alkoxide, or with alumina sol obtained from hydrolyzing aluminum alkoxide.
  • a film formed by applying the coating agent of the present invention has a microstructure wherein thin sheet microparticles 5 are layered in the film 1 in a uniform orientation and has high smoothness. Consequently, it is possible to form a film with high smoothness and adhesiveness to a base material. Due to high smoothness of the film, the surface area of the film becomes small, reducing the amount of contaminants adhering onto the film. However, even if contaminants adhere to the surface of the film, it is possible to decompose and remove the contaminants by the photocatalytic activity and superhydrophilic property of titanium oxide. Furthermore, hardness of the film is high.
  • a film formed by applying the coating agent of the present invention has the microstructure wherein thin sheet microparticle of titanium oxide are layered in a uniform orientation, it is possible to form an super-thin film compared to a film with the structure wherein spherical microparticles of titanium oxide are dispersed.
  • the particles in the present invention have sheet-like (thin sheet) shape the surface area of titanium oxide per unit volume is large. Therefore, a film formed by the coating agent of the present invention has a large contact area between a base material (an object on which coating agent is applied) and titanium oxide and high adhesiveness to the base material.
  • the coating agent of the present invention can easily form a film covering a large area by spin coat method or the like.
  • a film formed by the coating agent of the present invention has the superhydrophilic property. When water is in contact with the surface, it is difficult to form drops. Therefore, the film is advantageous in the antifogging of the surface.
  • the size of the above-described thin sheet microparticles of titanium oxide is preferred to be in the range of 0.1 to 10 ⁇ m.
  • the thickness thereof is preferred to be in the range of 0.3 to 3 nm, more preferably in the range of 0.5 to 1 nm.
  • aspect ratio of the thin sheet microparticles of titanium oxide is preferred to be in the range of 100 to 5000.
  • the ratio of the thin sheet microparticles of titanium oxide in the coating agent is preferred to be in the range of 0.025 to 10% by weight.
  • the invention in the claim 2 is related to the coating agent as set forth in the claim 1 wherein the coating agent contains silicon oxide sol prepared from tetra alkoxysilane.
  • the coating agent of the present invention can increase the adhesiveness between thin sheet microparticles of titanium oxide and a base material. Additionally, the coating agent of the present invention is advantageous in the chemical and physical stabilities compared to the coating agent wherein a resin binder is contained.
  • the coating agent of the present invention is different from the coating agent containing a resin binder, and capable of forming a film wherein inorganic substance is the major component (or only consists of inorganic substance) even at low temperature. Therefore, it is possible to form a hard film on resin and the like that is not resistant to heat.
  • the weight ratio of silicon oxide in the total weight of the coating agent is preferred to be in the range of 1 to 50% by weight. Particularly, if the weight ratio of silicon oxide is 5% by weight or more, it is possible to form a very hard film. Additionally, if the weight ratio of silicon oxide is 50% by weight or less, it is advantageous in the photocatalytic activity and the smoothness of the film.
  • the coating agent of the present invention can form a hard film even if the silicon oxide binder is contained in a small ratio, compared to the case wherein spherical microparticles of titanium oxide are used.
  • a conventional coating agent usually contains 50% by weight of the binder.
  • silicon oxide is used as a binder and 5% by weight in the blending quantity is enough to form a very hard film.
  • the invention in the claim 3 is related to the coating agent as set forth in the claim 1 wherein the coating agent contains titanium oxide sol prepared from titanium tetra alkoxide.
  • the coating agent of the present invention contains titanium oxide sol prepared from titanium tetra alkoxide, the adhesiveness between thin sheet microparticles of titanium oxide and a base material can be increased. Moreover, in the present invention, the chemical and physical stabilities of the coating agent are superior to a coating agent which contains resin binder.
  • the coating agent of the present invention is different from the coating agents containing a resin binder in the point that a film wherein titanium oxide is the major component (or only consists of titanium oxide) can be formed even at low temperature. Therefore, it is possible to form a film on a plastic and the like which is unresistant to heat.
  • the weight ratio of titanium oxide sol in the total weight of the coating agent is preferred to be in the range of 1 to 90% by weight. Particularly, when the ratio is 5% by weight or more, it is advantageous in the film hardness. Moreover, when the ratio is 90% by weight or lees, it is advantageous in the smoothness on the film.
  • the invention in the claims 4 is related to the coating agent as set forth in the claim 1 containing aluminum oxide sol prepared from aluminum alkoxide.
  • the coating agent of the present invention contains aluminum oxide sol prepared from aluminum alkoxide, the adhesiveness between the thin sheet microparticles of titanium oxide and a base material can be increased. Moreover, in the present invention, the chemical and physical stabilities of the coating agent are superior to the coating agent which contains rein binder.
  • the weight ratio of aluminum oxide sol in the total weight of the coating agent is preferred to be in the range of 1 to 50% by weight. Particularly, when the ratio is 5% by weight or more, it is advantageous in the film hardness. Moreover, when the ratio is 50% by weight or less, it is advantageous in the smoothness on the film.
  • the invention in the claim 5 is related to the coating agent as set forth in any of claims 1 to 4 furthermore containing the microparticles of titanium oxide in a shape other than the thin sheet shape in addition to the microparticles of titanium oxide in a thin sheet shape.
  • the coating agent of the present invention contains the microparticles of titanium oxide in other shapes in addition to the microparticles in a thin sheet shape, it is possible to form a hard film even if the calcination temperature after coating of the coating agent is low. Furthermore, even if the blending quantity of the thin sheet microparticles of titanium oxide in the coating agent is low, photocatalytic property can be maintained.
  • the coating agent of the present invention can be manufactured, for example, by dispersing microparticles of titanium oxide having the shapes other than the thin sheet shape, in anatase, rutile, or brookite, in solvent, such as ethanol, and mixing the solution with a coating agent wherein thin sheet microparticles of titanium oxide (for example, titania nanosheets) are dispersed.
  • the coating agent of the present invention can be also manufactured by adding microparticles of anatase, rutile and brookite and the like having the shapes other than the thin sheet shape to a coating agent wherein thin sheet microparticles of titanium oxide are dispersed.
  • microparticles other than the thin sheet shape there are, for example, spherical, needle-like, fibriform, platy, amorphous shapes and so on.
  • the blending ratio of thin sheet microparticles of titanium oxide and microparticles of titanium oxide in other shapes is preferred to be in the range of 99:1 to 10:90. Particularly, the range 90:10 to 50:50 is preferable.
  • the invention in the claim 6 is related to the coating agent as set forth in the claim 5 wherein the microparticles of titanium oxide in the shapes other than the thin sheet shape are microparticles of anatase, rutile or brookite.
  • the coating agent of the present invention is advantageous in a way that a hard film can be formed even if the calcination temperature after application of the coating agent is low, and in a way that photocatalytic property can be maintained even if the blending quantity of thin sheet microparticles of titanium oxide is low.
  • the invention in the claim 7 is related to the coating agent as set forth in any of the claims 1 to 6 wherein the roughness of the film surface formed by applying the coating agent onto a base material is in the range of 1 to 2 times the roughness of the surface of the base material.
  • the roughness of a film formed by applying the coating agent of the present invention is in the range of 1 to 2 times the roughness of the surface of a base material, and does not often become rough. Thus, the surface area of the film becomes small and the amount of contaminant adhered to the film becomes less.
  • Ra For the index of the roughness of the surface, Ra can be used.
  • AFM For a measurement device to obtain Ra, AFM can be used.
  • the invention in the claim 8 is related to the coating agent as set forth in any of the claims 1 to 7 wherein the hardness of a film formed by applying the coating agent of the present invention is determined by the nature of thin sheet particles of titanium oxide.
  • the hardness of a film formed by applying the coating agent is determined by the nature of thin sheet microparticles of titanium oxide. That is, even in a case wherein the coating agent of the present invention contains a binder, the film hardness does not depend upon the type of the binder (in other words, does not depend upon the fixation ability of the binder). Consequently, the coating agent of the present invention can form a film with high hardness irrespective of the type of a binder even if the coating agent contains a binder.
  • the invention in the claim 9 is related to the coating agent as set forth in any of the claim 1 to 8 wherein the reflectivity of a film formed by applying the coating agent on a base material is in the range of 90 to 120% of the reflectivity of the base material.
  • a film formed by applying the coating agent of the present invention does not reduce the reflectivity of a base material. Additionally, since the film formed by applying the coating agent of the present invention has the anti-staining, anti-fouling properties and self-cleaning property, the high reflectivity can be maintained.
  • the invention in the claim 10 is related to the coating agent as set forth in any of the claims 1 to 9 wherein the transmittance of the film formed by applying the coating agent on a transparent base material is in the range of 90 to 100% (particularly preferable in the range of 95 to 100%) of the transmittance of the base material.
  • the film formed by applying the coating agent of the present invention has high transmittance, and thus dose not change the color or texture of a base material.
  • the film is formed by applying the coating agent of the present invention on a coverglass of a solar battery or a light source, the film does not interrupt the incidence of the light due to high transmittance of the film. Consequently, it is possible to use the incident light effectively, and thus to effectively use the light energy.
  • the coating agent of the present invention is applied on a light transmitting section in a light sensor or an optical communication device, due to the high transmittance of the film formed thereon, it is possible to reduce the loss in optical communication.
  • a film formed by applying the coating agent of the present invention has the anti-staining, anti-fouling properties and self-cleaning property, high transmittance can be maintained.
  • the invention in the claim 11 is related to a film forming method comprising steps of applying the coating agent, and drying the coating agent as set forth in any of the claims 1 to 10 .
  • a film obtained by the present invention has high smoothness and adhesiveness to a base material, compared to the case wherein a coating agent in which only spherical microparticles of titanium oxide are dispersed is used. Therefore, the film has the anti-staining and anti-fouling properties wherein contaminants do not adhere to the film in the first place. Even when contaminants are adhered to the film, it is possible to decompose or to remove the contaminants with the aid of the photocatalytic property and the superhydrophilic property of titanium oxide.
  • titanium oxide in the present invention is thinly spread in a sheet-like shape, the surface area of titanium oxide per unit volume is large. Consequently, the film formed in the present invention has a large contact area between a base plate and titanium oxide, and high adhesiveness to a base material.
  • the invention in the claim 12 is related to the film forming method as set forth in the claim 11 wherein heating is conducted in the drying process.
  • the heating temperature is preferred to be in the range of 200 to 800° C.
  • the heating time is preferred to be in the range of 30 seconds to 2 hours.
  • the invention in the claim 13 is related to a titanium oxide film formed in accordance with the film forming method as set forth in the claim 11 or 12 .
  • titanium oxide is thinly spread in a sheet-like (thin sheet) shape, and thus the surface area of titanium oxide per unit volume is large. Consequently, the film of the present invention has a large contact area between a base material and titanium oxide and high adhesiveness to a base material.
  • the film of the present invention has the superhydrophilic property. Even when water is in contact with the surface, it is difficult to form drops. Therefore, the film is advantageous in the antifogging of the surface.
  • the invention in the claim 14 is related to the titanium oxide film as set forth in the claim 13 comprising a micro-structure wherein thin sheet microparticles of titanium oxide are layered in a uniform orientation.
  • the film of the present invention has a micro-structure wherein thin sheet microparticles of titanium oxide are layered in a uniform orientation, and has high smoothness. Therefore, the film has the anti-staining and anti-fouling properties by which contaminants are not easily adhered to the surface. Even contaminants are adhered to the film, it is possible to decompose and remove the contaminants with the aid of the photocatalytic property and the superhydrophilic property of titanium oxide. Furthermore, the film also has the high hardness.
  • the thickness of the film can be super-thin, compared to the structure wherein spherical microparticles of titanium oxide are dispersed.
  • the invention in the claim 15 is related to glass products comprising a base material made of glass and the film as set forth in the claim 13 or 14 formed on the surface of the base material.
  • the glass products of the present invention have high smoothness and anti-staining and anti-fouling properties. Even if contaminants are adhered to the glass product, it is possible to decompose and to remove the contaminants by the aid of the photocatalytic property and the superhydrophilic property of titanium oxide. Moreover, the adhesiveness between the film and a base material is high. Furthermore, since the film has the superhydrophilic property, even if water is in contact with the surface, it is difficult to form drops. Therefore, the glass product is advantageous in the antifogging of the surface.
  • glass for automobiles, glass for railway vehicles, glass for building materials, optical glasses, glass for lighting equipments, glass for mirrors, showcases, glass containers for food preservation, coverglass for solar batteries and glass for tanks can be given as examples of the glass products.
  • the invention in the claim 16 is related to metal products comprising a base material made of metal and the film as set forth in the claim 13 or 14 formed on the surface of the base material.
  • the metal products of the present invention have high smoothness, anti-staining and anti-fouling properties. Even if contaminants are adhered to the metal product, it is possible to decompose and remove the contaminants with the aid of the photocatalytic property and the superhydrophilic property of titanium oxide. Moreover, the adhesiveness between the film and a base material is high. Furthermore, since the film has the superhydrophilic property, even when water is in contact with the surface of the product, it is difficult to form drops. Therefore, the product is advantageous in the antifogging of the surface.
  • gates, iron fences, uncoated walls of railway vehicles, outer surface of aircrafts, aluminum wheels, aluminum building materials, stainless building materials can be given as examples of the metal products.
  • the invention in the claim 17 is related to ceramic products comprising a base material made of ceramic and the film as set forth in the claim 13 or 14 formed on the surface of the base material.
  • the ceramic products of the present invention Due to the film as set forth in the claim 13 or 14 , the ceramic products of the present invention have high smoothness, anti staining and anti-fouling properties. Even if contaminants are adhered to the ceramic product, it is possible to decompose and to remove the contaminants with the aid of the photocatalytic property and the superhydrophilic property of titanium oxide. Moreover, the adhesiveness between the film and a base material is high. Furthermore, since the film has the superhydrophilic property, even when water is in contact with the surface, it is difficult to form drops. Therefore, the ceramic product is advantageous in the antifogging property of the surface.
  • insulators, tiles, the dishes, sanitary goods, roof tiles can be given as examples of the ceramic products.
  • Ceramic for example, can be given.
  • Examples of a base material made of semiconductors can be, for example, silicon and germanium which are intrinsic semiconductors, P-type and N-type semiconductors wherein impurities are mixed therein.
  • Lasers, temperature sensors, and light sensors can be given as examples of the semiconductor products.
  • Carbon material for example, can be given as an example of the ceramic.
  • a base material made of a carbon material are, for example, carbon fiber, graphite, diamond and the like.
  • Examples of carbon material products are, for example, activated carbon, radio wave absorbing panels, carbon fiber sheets for reinforcing concrete, heat resistant window materials, radiating boards, electrodes and the like.
  • Nitride for example, can be another example of the ceramic.
  • a base material made of nitride are, for example, aluminum nitride, silicon nitride, titanium nitride, boron nitride and the like.
  • nitride products are, for example, heat resistant coatings, lasers, automobile engines, cutting tools and the like.
  • Carbide for example, can be some other example of the ceramic.
  • a base material made of carbide are, for example, silicon carbide, titanium carbide, tungsten carbide, boron carbide, zirconium carbide and the like.
  • carbide products are, for example, heat resistant coatings, molds, cutting tools, thermal materials, neutron absorbing materials.
  • the invention in the claim 18 is related to a heat resistant polymer products (heat resistant plastic products) comprising a base material made of a heat resistant polymer material and the film as set forth in the claim 13 or 14 formed on the surface of the base material.
  • the heat resistant plastic products of the present invention have high smoothness, anti-staining and anti-fouling properties. Even if contaminants are adhered to the heat resistant plastic product, it is possible to decompose and remove the contaminants with the aid of the photocatalytic property and the superhydrophilic property of titanium oxide. Moreover, the adhesiveness between the film and a base material is high. Furthermore, since the film has the superhydrophilic property, such that when water is in contact with the surface, it is difficult to form drops. The heat resistant plastic product is advantageous in the antifogging of the surface.
  • heat resistant plastic products plastic parts for automobiles, resin parts for cooking utensils, covers for high-power motors, resin parts for insulation and the like can be given.
  • the heat resistant polymer material composing a base material are, for example, epoxy resin, polyimide, silicon-base polymer, phenol resin.
  • FIG. 1 is a sectional view showing the structure of a film formed by a coating agent
  • FIG. 2 is a graph showing the test result related to the anti-staining, anti-fouling properties and self-cleaning property
  • FIG. 3 is a sectional view showing the structure of a film formed by a conventional coating agent.
  • Cesium carbonate was mixed with titanium oxide at a molar ratio of 1:5.3 and heated twice at 800° C. for 20 hours. Cesium titanate obtained was stirred in diluted hydrochloric acid, then filtered, and dried. After repeating this sequence of the processes four times, laminar titanic acid in which the cesium ion was converted into hydrogen ion was obtained. By adding hydrochloride solution of tetrabutylammonium to the titanic acid and stirring the game for 14 days, titania nanosheets are prepared.
  • Coating agent A 1 g of 4% by weight solution of titania nanosheet was dispersed into 2 g of ethanol so as to prepare ethanol solution of titania nanosheet which is to be referred to as Coating agent A.
  • sol solution of silicon oxide prepared by hydrolyzing tetraethoxysilane was dispersed in the above-described Coating agent A so as to make Coating agent B.
  • concentration of silicon oxide in the sol solution of silicon oxide is 0.4% by weight, and that the mixture ratio of the sol solution of silicon oxide and Coating agent A is 1:3. With this composition, the ratio of Si and Ti in Coating agent B becomes 1:9.
  • sol solution of titanium oxide is used instead of sol solution of silicon oxide
  • titanium tetraisopropoxide in place of the tetraethoxysilane
  • aluminum oxide is used instead of sol solution of silicon oxide
  • aluminum isopropoxide in place of the tetraethoxysilane.
  • Coating agent C for a comparative example 1, commercially available coating agent containing spherical titanium oxide (manufactured by Nippon Soda Co., Ltd., product name: Bistrator NRC-300L) was used as Coating agent C.
  • Coating agent A of the present embodiment 1 manufactured in accordance with the above-described a coating was conducted on a glass plate by the spin coat method. After sufficiently drying the coating film, the film was heated at 400° C. by a heat gun for one minute so as to be fixed on the glass plate. Formation of the film was confirmed by absorption spectrum measured by the ultraviolet-visible spectrophotometer and by the visual observation. After a few cycles of spin coating, drying and heating, a transparent thin film with larger thickness was formed. In the same way, other films were formed on glass plates by using Coating agent B and Coating agent C of the comparative example 1.
  • a glass product was manufactured having a film on the surface of a base material which is made of glass.
  • metallic base plate or ceramic base plate can be alternatively used in place of a glass base plate.
  • a metallic base plate is used, a metallic product is manufactured having a film on the surface of the base material which is made of metal.
  • a ceramic base plate is used, a ceramic product is manufactured having a film on the surface of the base material which is made of ceramic.
  • Coating agents A and B of the present embodiment can easily form a film covering a large area by the spin coat method and the like.
  • Coating agents A and B of the present embodiment are advantageous in chemical and physical stabilities as the coating agents do not need to contain a resin binder.
  • the film 1 formed with Coating agent B of the present embodiment 1 has an micro-structure wherein thin sheet microparticles of titanium oxide 5 are layered in a uniform orientation in a binder 7 , thus has high smoothness. Consequently, it is possible to make a super-thin film.
  • Coating agents A and B of the present embodiment 1 have high smoothness. Thus, contaminates are not easily adhered thereon. In other words, Coating agent A and B have high anti-staining and anti-fouling properties.
  • Films formed by Coating agents A and B have antibacterial property since the film can decompose and remove contaminants adhered thereon due to the photocatalytic activity attained by Coating agents A and B containing titanium oxide therein. Therefore, a film formed in accordance with the present embodiment 1 has self-cleaning property. Additionally, since the film has superhydrophilic property, the self-cleaning property of the film is even higher.
  • Films formed by Coating agents A and B of the present embodiment 1 have superhydrophilic property. Thus, even when water is in contact with the surface of the films, it is difficult to form drops. Consequently, the films are advantageous in the antifogging of the surface.
  • the shape of titanium oxide is thin sheet. This shape makes the contact area between titanium oxide and a base material large, and the adhesiveness between the film the base material high. As a result, the adhesiveness between the film and the base material becomes high, and the hardness of the film becomes high.
  • Coating agent B of the present embodiment 1 contains titanium oxide sol as a binder. Therefore, it is possible to form a film under low temperature and form a film on resin or the like which is unresistant to heat.
  • methylene blue 0.01 M aqueous solution of methylene blue trihydrate was prepared and applied on a film which was formed by Coating agent B of the present embodiment 1 by the spin coat method. The aqueous solution of MB was also applied in the same manner on a film which was formed with Coating agent C of the comparative example 1.
  • the amount of MB adhered on the films was measured.
  • the measurement was conducted respectively before and after the application of the aqueous solution of MB, and after 10 minutes exposure to the ultrahigh pressure mercury lamp. The result is shown in FIG. 2 .
  • the plot A shows measured values of the film formed by Coating agent B of the embodiment 1 before the application of the aqueous solution of MB on the film.
  • the plot B shows measured values of the film formed by Coating agent B immediately after the application of the aqueous solution of MB.
  • the plot C shows measured values of the film formed by Coating agent B of the embodiment 1 after the application of the aqueous solution of MB and the 10 minutes exposure to the ultrahigh pressure mercury lamp.
  • the plot D shows measured values of the film formed by Coating agent C of the comparative example 1 immediately after the application of the aqueous solution of MB.
  • the peak of the plot B which is the absorption of MB seen around 600 nm, is much smaller. That is, on the film formed by Coating agent B of the present embodiment 1, the amount of MB adhered thereto is much smaller than the amount of MB adhered to the film formed by Coating agent C of the comparative example 1. As a result, it was confirmed that the anti-staining and anti-fouling properties of the film formed by Coating agent B were high.
  • the plot C is approximately the same as the plot A.
  • the amount of MB adhered thereon decreased to an almost undetectable amount after the 10 minutes light exposure. Accordingly, it was confirmed that the film formed by Coating agent B of the present embodiment 1 had high photocatalytic activity, and was advantageous in the self-cleaning property.
  • the film hardness was evaluated. Specifically, first, a coating agent was repeatedly applied on a glass base plate 5 times, in the same manner as in the above-described (b), by the spin coat method so as to form a film which could be confirmed by the visual observation. Subsequently, the film was heated up to approximately 400° C. and calcined by a heat gun. Accordingly, a sample with fixed titanium oxide film was obtained. Film hardness was evaluated immediately after the coating and after the firing under the load of 750 g by the pencil scratch test machine.
  • Coating agent A and Coating agent B both prepared in the present embodiment 1 were used.
  • the film formed by Coating agent B after firing became a hard film with the hardness of 5H to 7H.
  • the film formed by Coating agent B without firing or the film formed by Coating agent A respectively turned out to be soft films with the hardness of 6B.
  • the superhydrophilic property of the film formed by Coating agent B of the present embodiment 1 was evaluated with a contact angle meter.
  • the contact angle was 58.0° before the light exposure, but became 3.0° after the light exposure indicating the superhydrophilic property of the surface.
  • the contact angle became larger, such as 16.0° after leaving the film in a dark place for 2 hours, 15.8° after 4 hours, 21.0° after 6 hours, and 39.0° after 24 hours, as the time passed.
  • the contact angle after 24 hours was still smaller than the original contact angle. This shows that the hydrophilic property was maintained for a long period of time.
  • alcohol dispersed liquid containing 4 wt % of titania nanosheets was prepared. This liquid was diluted with ethanol so as to make alcohol dispersed liquid containing 1 wt % of titania nanosheets.
  • this alcohol dispersed liquid containing 1 wt % of titania nanosheets and tetraethoxysilane (TEOS), a binder were mixed in accordance with the following compositions in the weight ratio so as to make the coating agents.
  • TNS/TEOS 100/0, 97.5/2.5, 95/5, 92.6/7.5, 90/10, 86/15, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, 0/100
  • TNS indicates the weight of titania nanosheets in the alcohol dispersed liquid containing 1 wt % of titania nanosheets
  • TEOS indicates the weight of tetraethoxysilane.
  • the prepared coating agents were respectively applied on Pyrex (registered trademark) glass in the size of 50 mm ⁇ 50 mm ⁇ thickness 3 mm by the spin coat method so as to form a film. Subsequently, firing was conducted at 100° C., 200° C., 300° C., 400° C., 600° C., 600° C., and 700° C. on those films formed by the coating agents with the ratio of TNS/TEOS 100/0, 97.5/2.5, 95/5, 92.5/7.5, 90/10, 85/15, 80/20, 70/30, 60/40, 50/60.
  • firing was conducted at 100° C., 200° C., 300° C., and 400° C. The firing was carried out once for one hour by an electric furnace.
  • Pencil scratch test firing temperature (° C.) composition 100 200 300 400 500 600 700 100/0 ⁇ 6B ⁇ 6B F >9H >9H >9H >9H 97.5/2.5 ⁇ 6B ⁇ 6B 6B 8H >9H >9H >9H 95/5 ⁇ 6B ⁇ 6B F >9H >9H >9H >9H 92.5/7.5 ⁇ 6B ⁇ 6B 3B >9H >9H >9H >9H >9H 90/10 ⁇ 6B ⁇ 6B 2B >9H >9H >9H 85/15 ⁇ 6B ⁇ 6B 6H >9H >9H >9H >9H 80/20 ⁇ 6B ⁇ 6B F >9H >9H >9H >9H >9H >9H 70/30 ⁇ 6B ⁇ 6B 7H >9H >9H >9H >9H >9H 60/40 ⁇ 6B ⁇ 6B 7H >9H >9H >9H >9H 50/50 ⁇ 6
  • the film hardness became equal to or harder than 9H which was the hardest, irrespective of the composition ratio of TNS and the binder when firing was conducted at or higher than 400° C. In these cases, the films became particularly hard.
  • Adhesiveness test firing temperature (° C.) composition 100 200 300 400 500 600 700 100/0 2 4 10 10 10 10 97.5/2.5 2 4 10 10 10 10 10 95/5 2 4 10 10 10 10 10 92.5/7.5 0 8 10 10 10 10 10 90/10 0 10 10 10 10 10 10 10 85/15 0 10 10 10 10 10 10 10 80/20 2 10 10 10 10 10 10 10 10 10 70/30 4 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 50/50 8 10 10 10 10 10 10 40/60 6 8 10 10 30/70 6 8 10 10 20/80 8 8 10 10 10/90 8 10 10 10 10
  • the surface became superhydrophilic wherein the contact angle is equal to or smaller than 10 degree, irrespective of the composition ratio of the TNS and the binder as a result of the firing at or higher than 200° C. Moreover, when the firing temperature was 300° C. or higher, the hydrophilic property was even better. Furthermore, when the firing temperature was 400° C. or higher, the hydrophilic property was even better.
  • the anti-staining and anti-fouling properties became high when the firing temperature was at or higher than 300° C.
  • the amount of MB adhered on the film was approximately 2.
  • the film obtained better property as a result of firing at higher temperature.
  • the ratio of the binder was low (for example, when the ratio of the binder is smaller than 90/10), the anti-staining and anti-fouling properties were even higher.
  • MB was adhered onto a film by immersing the film into 0.1 mM methylene blue (MB) aqueous solution overnight and washing the film with pure water after taking out the film from the solution. Subsequently, the film was exposed to the light from the ultrahigh pressure mercury lamp for 10 minutes. Then the residual amount of MB on the film was measured. The amount of adhered MB is indicated as the size of absorption area. The result is shown in Table 5.
  • composition rate of methylene blue by ultraviolet ray exposure firing temperature (° C.) composition 100 200 300 400 500 600 700 100/0 0.69 0.83 0.89 0.84 0.88 0.79 0.62 97.5/2.5 0.73 0.83 0.68 0.97 0.86 0.82 0.79 95/5 0.70 0.85 0.86 0.92 0.80 0.84 0.81 92.5/7.5 0.54 0.85 0.81 0.95 0.91 0.90 0.85 90/10 0.52 0.85 0.79 0.91 0.86 0.78 0.83 85/15 0.53 0.83 0.78 0.94 0.93 0.90 0.99 80/20 0.65 0.84 0.77 0.97 0.93 0.89 0.92 70/30 0.62 0.84 0.65 0.78 0.92 0.92 0.65 60/40 0.72 0.83 0.47 0.94 0.94 0.95 0.91 50/50 0.73 0.81 0.87 1.00 0.95 0.92 0.94 40/60 0.64 0.66 0.51 0.57 30/70 0.61 0.60 0.49 0.55 20/80 0.64 0.64 0.50 0.51 10/90 0.67 0.65 0.49 0.47
  • alcohol dispersed solution containing 1 wt % titania nanosheets was prepared.
  • the solution was diluted with ethanol so as to make alcohol dispersed solution containing 0.25 wt % titania nanosheets.
  • the alcohol dispersed solution containing 0.25 wt % titania nanosheets and titanium tetraisopropoxide (TIPO), a binder were mixed together in accordance with the following compositions in the weight ratio so as to make coating agents.
  • TNS/TIPO 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90
  • TNS indicates the weight of titania nanosheets in the alcohol dispersed solution containing 0.25 wt % titania nanosheets
  • IPO indicates the weight of titanium tetraisopropoxide.
  • the prepared coating agents were respectively applied on Pyrex (registered trademark) glass in the size of 50 mm ⁇ 50 mm ⁇ thickness 3 mm. Firing was conducted at 100° C., 200° C., 300° C., 400° C., 500° C., and 600° C. so as to form a film.
  • Adhesiveness test firing temperature (° C.) composition 100 200 300 400 500 600 90/10 2 2 10 10 10 10 80/20 2 2 10 10 10 10 10 70/30 2 2 10 10 10 10 10 10 10 60/40 2 6 10 10 10 10 10 50/50 2 6 10 10 10 10 10 40/60 2 6 10 10 10 10 10 30/70 4 6 10 10 10 10 20/80 4 6 10 10 10 10/90 8 8 10 10 10 10 10
  • composition rate of methylene blue by ultraviolet ray exposure firing temperature (° C.) composition 100 200 300 400 500 600 90/10 0.69 0.24 0.68 0.80 0.85 0.86 80/20 0.46 0.56 0.61 0.63 0.88 0.88 70/30 0.46 0.49 0.68 0.72 0.72 0.61 60/40 0.49 0.55 0.80 0.87 0.89 0.88 50/50 0.54 0.42 0.68 0.78 0.78 0.65 40/60 0.31 0.44 0.83 0.89 0.61 0.57 30/70 0.32 0.40 0.85 0.77 0.62 0.29 20/80 0.33 0.24 0.99 0.83 0.80 0.71 10/90 0.31 0.41 0.89 0.84 0.72 0.88
  • the film hardness improved as the ratio of the binder increased. Moreover, higher firing temperature resulted with higher hardness.
  • TNS/TIPO was 90/10, 80/20, 70/30, and 60/40, the hardness became the highest, 9H or higher at the firing temperature of 500° C. or higher.
  • TNS/TIPO was 50/50, 40/60, 30/170, 20/80, and 10/90, the hardness became the highest, 9H or harder at the firing temperature of 300° C. or higher.
  • the hydrophilic property became superhydrophilic wherein the contact angle is 10 degree or smaller by firing at 300° C. or higher irrespective of the composition ratio of TNS and the binder.
  • the anti-staining and anti-fouling properties were particularly good, wherein the amount of adhered MB was approximately 2, when the firing temperature was at or higher than 300° C. Firing at higher temperature made the film better in the anti-staining and anti-fouling properties. Even when the binder ratio was increased, the anti-staining and anti-fouling properties were not reduced.
  • the ability to decompose fouling was particularly good when the firing temperature was at or higher than 300° C. irrespective of the composition ratio of the TNS and the binder.
  • alcohol dispersed solution containing spherical titanium oxide powder at the concentration of 1 wt % (product name: ST-01, manufactured by Ishihara Sangyo Kaisha, Ltd.) wherein the size of primary particles was 7 nm was also prepared.
  • ST-01 manufactured by Ishihara Sangyo Kaisha, Ltd.
  • this ST-01 mainly contains anatase.
  • the alcohol dispersed solution of titania nanosheets and the alcohol dispersed solution of spherical titanium oxide powder were mixed at the following volume ratios so as to make coating agents.
  • TNS/ST-01 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, and 10/90
  • the coating agents prepared as above contains microparticles of titanium oxide having other shapes (spherical).
  • TNS indicates the volume of the alcohol dispersed solution containing titania nanosheets
  • ST-01 indicates the volume of the alcohol dispersed solution containing spherical titanium oxide.
  • the prepared coating agents were respectively applied on Pyrex (registered trademark) glass in the size of 50 mm ⁇ 50 mm ⁇ thickness 3 mm. Firing was subsequently conducted at 200° C., 300° C., 400° C., 500° C., and 600° C. so as to form a film.
  • composition rate of methylene blue by ultraviolet ray exposure firing temperature (° C.) composition 200 300 400 500 600 90/10 0.62 0.74 0.86 0.86 0.82 80/20 0.87 0.94 0.87 0.85 0.86 70/30 0.71 0.75 0.81 0.90 0.85 60/40 0.76 0.77 0.80 0.87 0.89 50/50 0.72 0.87 0.90 0.84 0.80 40/60 0.70 0.86 0.83 0.89 0.80 30/70 0.66 0.79 0.84 0.81 0.75 20/80 0.68 0.75 0.79 0.81 0.78 10/90 0.69 0.80 0.84 0.84 0.77
  • the highest film hardness, 9H or harder was attained by the firing temperature of 300° C. or higher.
  • the films formed when was 20/80, and 10/90, the highest film hardness, 9H or harder was attained by the firing temperature of 400° C. or higher.
  • the hydrophilic property of the film become superhydrophilic, wherein the contact angle is 10 degree or smaller, by firing at or higher than 200° C. irrespective of the composition of TNS/ST-01.
  • the anti-staining and anti-fouling properties were even better, wherein the amount of adhered MB was approximately 2, when the firing temperature was at or higher than 300° C. Firing at higher temperature made the films better in the anti-staining and anti-fouling properties.
  • the ability to decompose fouling of the film was particularly good when the firing temperature was at or higher than 300° C. irrespective of the composition ratio of TNS/ST-01.
  • the coating agents of the present embodiment 4 contains spherical titanium oxide powder, even coating agents, wherein the mixing ratio of the binder is low, can achieve the pencil scratch hardness of 9H at the low firing temperature of 300° C.
  • the coating agents of the present embodiment 4 it is possible with the coating agents of the present embodiment 4 to reduce the mixing ratio of the binder while maintaining the high hardness. In such case, it is possible to increase the anti-staining, anti-fouling properties and ability to decompose fouling to A higher degree.
  • the coating agents of the present embodiment 4 can achieve high photocatalytic activity (superhydrophilic property, capability of oxidized decomposition) even when the ratio of the titania nanosheets is low.
  • the smoothness of the films formed in the above-described embodiment 1 was evaluated with AFM.
  • model SPA 300 manufactured by SII Nano Technology Inc. was used for the measurement apparatus of the evaluation.
  • the measurement condition was set in the tapping mode.
  • the roughness Ra of the surface of the film formed in the above-described embodiment 1 was 0.4 nm.
  • the roughness of the glass surface prior to the formation of the film was 0.2 to 0.3 nm. Therefore, it was confirmed that the smoothness was not lost even the coating agent was applied and a film was formed.
  • alcohol dispersed solution containing 1 wt % titania nanosheets was prepared, and then diluted with ethanol so as to make alcohol dispersed solution containing 0.25 wt % titania nanosheets.
  • This alcohol dispersed solution was applied on the surface of a high reflective aluminum mirror (manufactured by Material House Co., Ltd.). Then, firing was conducted at each temperature indicated in Table 15 which is to be described hereinafter. Subsequently, the reflectance of the part on which the alcohol dispersed solution was applied was measured in the regular reflection with the incidence angle of 5° by the ultraviolet-visible spectrophotometer.
  • the reflectance standard was the reflectance of the evaporated aluminum film attached to the ultraviolet-visible spectrophotometer. The results of the measurements are shown in Table 15.
  • alcohol dispersed solution containing 1 wt % titania nanosheets was prepared and diluted with ethanol so as to make alcohol dispersed solution containing 0.25 wt % titania nanosheets.
  • This alcohol dispersed solution and tetraethoxysilane (TEOS), a binder were mixed in accordance with the following composition in the weight ratio so as to make coating agents.
  • TNS/TEOS-10010 90/10, 80/20, 70/30, 60/40, 40/60, 30/70, 20/80, and 10/90
  • TNS indicates the weight of titania nanosheets in the alcohol dispersed solution containing 0.25 wt % titania nanosheets
  • TEOS indicates the weight of tetraethoxysilane.
  • the prepared coating agents were respectively applied on Pyrex (registered trademark) glass in the size of 50 mm ⁇ 50 mm ⁇ thickness 3 mm by the spin coat method. Subsequently, firing was conducted at 400° C. so as to form a film. The transmittance of the portion on the glass wherein the film was formed was measured with the ultraviolet-visible spectrophotometer. The results are shown in Table 16.
  • the transmittance indicated above is the average of the transmittance of the light in the visible light area (400 to 800 nm) in regard to the base material. As shown in Table 16, it was confirmed that the average transmittance is 96.8%, and that the transmittance hardly decreases even when a coating agent was applied and the film is formed.
  • the above-mentioned “average transmittance” means the average value of the transmittance shown in Table 16.
  • Uncoated Pyrex (registered trademark) glass in the size of 50 mm ⁇ 50 mm ⁇ thickness 3 mm was immersed into 0.1 mM MB aqueous solution overnight and cleansed with distilled water.
  • the amount of MB initially adhered was 2.1. This amount is comparable or more than the amount adhered to the base plate on which 1 wt % titania nanosheets coating was applied. Therefore, by comparing with this comparative example 2, it was confirmed that the films formed by applying the coating agents in the above-described embodiments 2 to 4 either do not reduce the anti-staining and anti-fouling properties of the original base material or improve the anti-staining and anti-fouling properties.
  • Pencil scratch test Sample Pencil hardness ST-K211 - rt - dip 3H ST-K211 - 100° C. - dip 5H ST-K211 - 300° C. - dip 8H ST-K211 - 400° C. - dip >9H ST-K211 - 500° C. - dip >9H
  • the anti-staining and anti-fouling properties show 3 or higher in all the conditions.
  • the films formed in the test were easy to be stained compared to the result of the above-described embodiments 2 to 4.
  • the smoothness of the film formed by the above-described comparative example 3 was evaluated in the same manner as in the above-described embodiment 5.
  • the roughness Ra of the surface of the film formed in the above-described comparative example 3 was 3.5 nm. Compared to this value, the roughness of the surface of the glass prior to forming a film thereon was 0.2 to 0.3 nm. Consequently, it was confirmed that the smoothness of a base material was reduced when a film was formed by applying the coating agent of the above-described comparative example 3.
  • the film formed by Coating agent B has equivalent effect in the anti-staining, anti-fouling properties, self-cleaning property and the like.
  • metal, semiconductors, carbon materials, nitride or carbide for the base materials, metal products, semiconductor products, carbon material products, nitride products, or carbide products may be manufactured.
  • titanium oxide for mixing that it in the shapes other than the thin sheet shape may be any of the titanium oxide among anatase, rutile, and brookite. Furthermore, the titanium oxide may be a composite of two or more types of titanium oxide selected from the above-mentioned three types.

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US20120067401A1 (en) * 2009-02-04 2012-03-22 Takahisa Kusuura Variable light condensing lens apparatus and solar cell apparatus
US8404964B2 (en) * 2009-02-04 2013-03-26 Empire Technology Development Llc Variable light condensing lens apparatus and solar cell apparatus
US10575370B2 (en) 2015-09-25 2020-02-25 Samsung Electronics Co., Ltd. Electrical conductors, electrically conductive structures, and electronic devices including the same
US10937857B2 (en) 2019-02-14 2021-03-02 Samsung Electronics Co., Ltd. Single crystal material and method of forming the same and stacked structure and ceramic electronic component and device
US11664414B2 (en) 2019-02-14 2023-05-30 Samsung Electronics Co., Ltd. Single crystal material and method of forming the same and stacked structure and ceramic electronic component and device

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TWI377176B (enrdf_load_stackoverflow) 2012-11-21
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